Black iron-based particles and black toner containing the same

ABSTRACT

Black iron-based particles comprise a FeTiO 3 —Fe 2 O 3  solid solution or a mixed composition of a FeTiO 3 —Fe 2 O 3  solid solution and an iron-based oxide having a spinel structure, and having a Ti content of from more than 10.0 atm % to 40.0 atm %, calculated as Ti, based on whole Fe, and a blackness (L* value) of 6 to 13.

BACKGROUND OF THE INVENTION

The present invention relates to black iron-based particles and a blacktoner containing the black iron-based particles, and more particularly,to black iron-based particles having not only an excellent blackness butalso a less magnetization value, and a black toner containing the blackiron-based particles, which has not only an excellent blackness but alsoa low magnetization value.

The black iron-based particles of the present invention are used asblack-colored pigments and paints, colorants for resin compositions,etc., and, in particular, are applicable to black non-magnetic toners.

Hitherto, black pigments such as magnetite particles, ilmenite particlesand carbon black have been generally used as colorants for paints,printing inks, cosmetics, rubbers, resin compositions or the like.

In particular, composite particles prepared by mixing-dispersing blackmagnetic iron oxide particles such as magnetite particles in resins havebeen more frequently used for a magnetic toner as an electrophotographicdeveloper.

With recent tendency to high-speed copying operation and high-imagequality for laser beam printers or digital copying machines, it has beenstrongly required to improve properties of a black toner used as adeveloper. In particular, the black toner has been strongly required tohave a sufficient blackness.

Separately, in recent years, with the progress of full color printingand copying techniques, non-magnetic toners have been used in the fieldsof printers or copying machines.

Thus, in the field of such black toners, it has also been demanded toprovide black non-magnetic toners having non-magnetic properties or amuch less magnetization value which are suitably applicable to thecurrent developing systems.

Although, as described above, it has been strongly required to improvevarious properties of the black toners, it is known that the blacktoners, especially black pigments contained therein, have significantinfluences on developing characteristics. That is, since the propertiesof the black toners have a close relationship with those of the blackpigments mixed and dispersed therein, it has also been strongly requiredto further improve properties of the black pigments used in the blacktoners.

Namely, in order to obtain black toners exhibiting an excellentblackness, black particles used therein have been required to show asufficient blackness and an excellent dispersibility. Also, in order tosuitably apply the black toners to the current developing systems usingnon-magnetic toners, the black particles used therein have also beenrequired to be particles having non-magnetic properties or a much lessmagnetization value.

It is known that since carbon black as non-magnetic particles is in theform of fine particles having an average particle diameter of about0.005 to 0.05 μm, it may be difficult to disperse the carbon black invehicle or resin compositions. In addition, it is also known that sincethe carbon black is in the form of bulky particles having a bulk densityof about 0.1 g/cm³, the carbon black is poor in handling property andworkability.

Thus, it has been required to provide black particles having anexcellent blackness and a low magnetization value. The low magnetizationvalue (saturation magnetization value) used herein means that themagnetization value (saturation magnetization value) is minimized so asto be applicable to the current developing systems, more specifically,is usually not more than 60 Am²/kg, preferably not more than 40 Am²/kg.

As the black-colored iron-based particles, there are known ilmeniteparticles obtained by hydrothermal treatment (Japanese PatentApplication Laid-Open (KOKAI) No. 1-298028(1989)); black pigmentparticles having a mixed composition composed of Fe₂TiO₅ andFe₂O₃—FeTiO₃ solid solution (Japanese Patent Application Laid-Open(KOKAI) No. 3-2276(1991)); black magnetic iron oxide particles having amagnetization value σ₁₀₀₀ (at a magnetic field of 1 kOe) of 20 to 50Am²/kg, and containing titanium in an amount of 0.5 to 10.0 atm % basedon whole Fe (Japanese Patent Application Laid-Open (KOKAI) No.8-34617(1996)); and titanium-containing magnetite particles (JapanesePatent Application Laid-Open (KOKAI) No. 2002-196528).

Although, at present, it has been strongly required to provide blackiron-based particles having an excellent blackness and a lessmagnetization value, such particles have not been obtainedconventionally.

That is, in Japanese Patent Application Laid-Open (KOKAI) No.1-298028(1989), it is described that the ilmenite particles are producedby hydrothermal treatment using Ti³⁺. However, the production of theilmenite particles by hydrothermal treatment is disadvantageous fromindustrial viewpoints.

Although the non-magnetic particles described in Japanese PatentApplication Laid-Open (KOKAI) No. 3-2276(1991) contain Fe₂TiO₅ and,therefore, have a low magnetization value, such particles have a lowtinting strength and, therefore, fail to show a sufficient blackness, asshown in the below-mentioned Comparative Examples.

The black magnetic iron oxide particles described in Japanese PatentApplication Laid-Open (KOKAI) No. 8-34617(1996) have a Ti content of 0.5to 10 atm % and a magnetization value σ₁₀₀₀ at a magnetic field of 1 kOeas high as 20 to 50 emu/g and, therefore, fail to sufficiently apply tothe current non-magnetic developing systems.

In Japanese Patent Application Laid-Open (KOKAI) No. 2002-196528, thereis described that the black toner containing a metal oxide has amagnetization value of not more than 40 emu/g. However, sinceTi-containing magnetite particles having a large average particlediameter were used as the metal oxide in Examples, the obtained blacktoner fails to show a satisfactory tinting strength.

As a result of the present inventors' earnest studies, it has been foundthe following matters. Upon production of the black iron-basedparticles, it is important to add a titanium compound to a watersuspension of magnetite particles for coating the surface of themagnetite particles with the titanium compound (titanium oxidehydroxide). In order to form the coat of the titanium oxide hydroxide,it is necessary to allow the water suspension to maintain its pH valuewithout lowering thereof, obtained immediately after adding the titaniumcompound thereto. When the magnetite particles coated with the titaniumoxide hydroxide are heat-calcined at a specific temperature under anon-oxidative atmosphere, and then pulverized, the obtained particlescan unexpectedly show not only an excellent blackness but also a lowmagnetization value. The present invention has been attained on thebasis of the above findings.

SUMMARY OF THE INVENTION

An object of the present invention is to provide black iron-basedparticles having not only an excellent blackness but also a lessmagnetization value.

Another object of the present invention is to provide a black tonerhaving not only an excellent blackness but also a less magnetizationvalue.

To accomplish the aims, in the first aspect of the present invention,there are provided black iron-based particles comprising a FeTiO₃—Fe₂O₃solid solution or a mixed composition of a FeTiO₃—Fe₂O₃ solid solutionand an iron-based oxide having a spinel structure, and having a Ticontent of from more than 10.0 atm % to 40.0 atm %, calculated as Ti,based on whole Fe, and a blackness (L* value) of 6 to 13.

In the second aspect of the present invention, there are provided blackiron-based particles comprising (1) a FeTiO₃—Fe₂O₃ solid solution or amixed composition of a FeTiO₃—Fe₂O₃ solid solution and an iron-basedoxide having a spinel structure, and (2) a Na—Fe—Ti compound, and havinga Ti content of from more than 10.0 atm % to 40.0 atm %, calculated asTi, based on whole Fe, and a blackness (L* value) of 6 to 13.

In the third aspect of the present invention, there are provided blackiron-based particles comprising (1) a FeTiO₃—Fe₂O₃ solid solution or amixed composition of a FeTiO₃—Fe₂O₃ solid solution and an iron-basedoxide having a spinel structure, and (2) a blue pigment, and having a Ticontent of from more than 10.0 atm % to 40.0 atm %, calculated as Ti,based on whole Fe, and a blackness (L* value) of 6 to 13.

In the fourth aspect of the present invention, there are provided blackiron-based particles comprising (1) a FeTiO₃—Fe₂O₃ solid solution or amixed composition of a FeTiO₃—Fe₂O₃ solid solution and an iron-basedoxide having a spinel structure, (2) a Na—Fe—Ti compound, and (3) a bluepigment, and having a Ti content of from more than 10.0 atm % to 40.0atm %, calculated as Ti, based on whole Fe, and a blackness (L* value)of 6 to 13.

In the fifth aspect of the present invention, there are provided blackiron-based particles a FeTiO₃—Fe₂O₃ solid solution or a mixedcomposition of a FeTiO₃—Fe₂O₃ solid solution and an iron-based oxidehaving a spinel structure, and having a Ti content of from more than10.0 atm % to 40.0 atm %, calculated as Ti, based on whole Fe, ablackness (L* value) of 6 to 13, a saturation magnetization value of 5to 40 Am²/kg and an average particle diameter of 0.04 to 0.24 μm.

In the seventh aspect of the present invention, there are provided blackiron-based particles comprising:

-   -   (1) a FeTiO₃—Fe₂O₃ solid solution or a mixed composition of a        FeTiO₃—Fe₂O₃ solid solution and an iron-based oxide having a        spinel structure, and (2) a Na—Fe—Ti compound,    -   and having a Ti content of from more than 10.0 atm % to 40.0 atm        %, calculated as Ti, based on whole Fe, a saturation        magnetization value of 0.1 to 60 Am²/kg, a blackness (L* value)        of 6 to 13 and an average particle diameter of 0.04 to 0.24 μm,        said Na—Fe—Ti compound being contained in such an amount that a        ratio of a main peak intensity of the Na—Fe—Ti compound to a        peak intensity of (104) plane of FeTiO₃—Fe₂O₃ is 0.01:1 to        1.00:1, when measured by an X-ray diffraction method.

In the eighth aspect of the present invention, there are provided blackiron-based particles comprising:

-   -   (1) 80 to 99.9 parts by weight of a FeTiO₃—Fe₂O₃ solid solution        or a mixed composition of a FeTiO₃—Fe₂O₃ solid solution and an        iron-based oxide having a spinel structure; and (2) 0.1 to 20        parts by weight of a blue pigment,    -   and having a Ti content of from more than 10.0 atm % to 40.0 atm        %, calculated as Ti, based on whole Fe, a saturation        magnetization value of 5 to 40 Am²/kg, a blackness (L* value) of        6 to 13 and an average particle diameter of 0.04 to 0.24 μm.

In the ninth aspect of the present invention, there is provided a blacknon-magnetic toner comprising a binder resin and the black iron-basedparticles as defined in any one of the above aspects.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is an electron micrograph (magnification: 20,000) showing blacknon-magnetic particles obtained in Example 1.

FIG. 2 is an X-ray diffraction pattern of the black non-magneticparticles obtained in Example 1.

FIG. 3 is an X-ray diffraction pattern of black non-magnetic particlesobtained in Comparative Example 1.

FIG. 4 is an X-ray diffraction pattern of the black non-magneticparticles obtained in Example 34.

DETAILED DESCRIPTION OF THE INVENTION

The present invention is described in detail below.

First, the black iron-based particles according to the present inventionare explained.

The black iron-based particles according to the present inventioncomprises (1) a FeTiO₃—Fe₂O₃ solid solution or (2) a mixed compositionof a FeTiO₃—Fe₂O₃ solid solution and an iron-based oxide having a spinelstructure. The iron-based oxide having a spinel structure may beconstituted by a Fe₃O₄-γ-Fe₂O₃ solid solution. When only Fe₂O₃ iscontained, i.e., no FeTiO₃ is contained, the obtained particles tend toexhibit a red color and, therefore, tend to fail to exhibit the aimedblackness. Also, when only FeTiO₃ is contained, i.e., no Fe₂O₃ iscontained, such particles may require a heat treatment at a highertemperature, so that the obtained particles tend to have a largeparticle diameter, thereby failing to attain a sufficient tintingstrength.

The black iron-based particles of the present invention contain theFe₃O₄-γ-Fe₂O₃ solid solution in such an amount that a ratio of a peakintensity of (220) plane of Fe₃O₄-γ-Fe₂O₃ to a peak intensity of (104)plane of FeTiO₃—Fe₂O₃ is usually 1:0.01 to 1:0.5, preferably 1:0.05 to1:0.45, when measured by an X-ray diffraction method as describedhereinafter. When the peak intensity ratio is 1:0.5 or more, theobtained particles tend to have a high magnetization value, so that itmay be difficult to apply the particles to the current developingsystems using non-magnetic toners.

The black iron-based particles of the present invention have a Ticontent of usually from more than 10.0 atm % to 40.0 atm %, preferably12 to 35 atm %, more preferably 20 to 33.3 atm % based on the whole Fe.When the Ti content is not more than 10.0 atm %, the obtained particlestend to have a high magnetization value, so that it may be difficult toapply the particles to the current developing systems using non-magnetictoners. When the Ti content is more than 40.0 atm %, an unreacted Ticompound tends to remain in the obtained particles, thereby failing toattain the aimed blackness and tinting strength.

The black iron-based particles of the present invention have a blackness(L* value) of usually 6 to 13, preferably 6 to 12.5, more preferably 6to 11.5. When the blackness (L* value) is more than 13, the obtainedparticles tend to fail to show a sufficient blackness and, therefore,may be unusable as a black pigment. On the other hand, it is notpossible to industrially produce such particles having a blackness (L*value) of less than 6.

The black iron-based particles of the present invention have asaturation magnetization value of usually not more than 60 Am²/kg,preferably 0.1 to 40 Am²/kg, more preferably 5 to 30 Am²/kg, still morepreferably 5 to 25 Am²/kg. When the saturation magnetization value ismore than 60 Am²/kg, it may be difficult to apply the obtained particlesto the current developing systems using non-magnetic toners, and furtherthe obtained toner image tends to fail to exhibit a sufficient imagedensity, and tends to suffer from fogging.

The black iron-based particles of the present invention have an averageparticle diameter of usually 0.01 to 0.50 μm preferably 0.04 to 0.24 μm,more preferably 0.08 to 0.20 μm. When the average particle diameter isless than 0.01 μm, the obtained particles tend to fail to show asufficient blackness. When the average particle diameter is more than0.5.0 μm, the obtained particles tend to fail to show a sufficienttinting strength.

The black iron-based particles of the present invention have a BETspecific surface area value of usually 3 to 30 m²/g, preferably 6 to 30m²/g, more preferably 6.5 to 20 m²/g. When the BET specific surface areavalue is less than 3 m²/g, the obtained black non-magnetic particlestend to become coarse, or sintering within or between the particlestends to be caused, resulting in production of coarse particles having apoor tinting strength. When the BET specific surface area value is morethan 30 m²/g, it may be difficult to obtain particles having asufficient blackness.

The black iron-based particles of the present invention have a tintingstrength of usually 35 to 45, preferably 35 to 44, when measured by thebelow-mentioned drawdown evaluation method. When the tinting strength ismore than 45, a black non-magnetic toner prepared from the blacknon-magnetic particles tends to fail to form a toner image having asufficient image density. It may not be possible to industrially produceblack non-magnetic particles having a tinting strength of less than 35.

The black iron-based particles of the present invention may furthercontain a Na—Fe—Ti compound. The black iron-based particles containingthe Na—Fe—Ti compound can be further improved in blackness. Therefore,the black iron-based particles containing the Na—Fe—Ti compound can showa sufficient blackness even though Fe₂TiO₅ is included therein.

Examples of the Na—Fe—Ti compound may include NaFeTi₃O₈, NaFeTiO₄,Na_(0.75)Fe_(0.75)Ti_(0.25)O₂ or the like.

The amount of sodium contained in the black iron-based particles isusually not more than 10% by weight, preferably 0.01 to 7% by weight.When the sodium content is more than 10% by weight, the particlesobtained after the calcination tend to contain an increased amount ofthe iron-based oxide having a spinel structure, so that it may bedifficult to attain the desired magnetization value.

The amount of the Na—Fe—Ti compound may be contained in the blackiron-based particles in such an amount that a ratio of a main peakintensity of the Na—Fe—Ti compound to a peak intensity of (104) plane ofFeTiO₃—Fe₂O₃ is preferably 0.01:1 to 1.00:1, more preferably 0.01:1 to0.7:1, still more preferably 0.01:1 to 0.5:1, when measured by an X-raydiffraction method as described hereinafter. When the peak intensityratio is more than 1.00:1, the obtained particles tend to exhibit a highmagnetization value, so that it may be difficult to apply the particlesto the current developing systems using non-magnetic toners. Meanwhile,the “main peak” used herein means such a peak having a maximum peakintensity in X-ray diffraction. For example, the main peak of NaFeTi₃O₈is a peak observed at a spacing (d) of 3.63 Å, the main peak of NaFeTiO₄is a peak observed at (112) plane thereof, and the main peak ofNa_(0.75)Fe_(0.75)Ti_(0.25)O₂ is a peak observed at (104) plane thereof.

The black iron-based particles containing the Na—Fe—Ti compound havesubstantially the same Ti content and average particle diameter as thoseof the above-mentioned black iron-based particles containing no Na—Fe—Ticompound. Further, the black iron-based particles containing theNa—Fe—Ti compound have a magnetization value of preferably 0.1 to 60Am²/kg, more preferably 0.1 to 40 Am²/kg, a blackness (L* value) ofpreferably 6 to 12, more preferably 6 to 11, and a tinting strength ofpreferably 35 to 43.5, when measured by the below-mentioned drawdownevaluation method.

The black iron-based particles of the present invention may contain ablue pigment. In the blue pigment-containing black iron-based particles,the blue pigment may be present with the FeTiO₃—Fe₂O₃ solid solution (1)or the mixed composition (2) composed of FeTiO₃—Fe₂O₃ solid solution andthe iron-based oxide having a spinel structure. Alternatively, the bluepigment may be adhered on the surface of each particle composed of theFeTiO₃—Fe₂O₃ solid solution, or the mixed composition of theFeTiO₃—Fe₂O₃ solid solution and the iron-based oxide having a spinelstructure. The black iron-based particles having the blue pigment can befurther improved in blackness and tinting strength.

The amount of the blue pigment is usually not more than 20% by weight,preferably 0.1 to 20% by weight, more preferably 1 to 10% by weight.When the blue pigment content is more than 20%, the obtained particlestend to exhibit a hue closer to that of the blue pigment due to toolarge amount of the blue pigment, thereby failing to show the desiredblackness.

The black iron-based particles having the blue pigment havesubstantially the same composition, average particle diameter andmagnetization value as those of the above-mentioned black iron-basedparticles having no blue pigment. More specifically, the blackiron-based particles having the blue pigment, have a blackness (L*value) of preferably 6 to 12, more preferably 6 to 11, and a tintingstrength of preferably 30 to 42, when measured by the below-mentioneddrawdown evaluation method.

The blue pigment used in the present invention is not restricted toparticular ones. Examples of the blue pigment may include known bluepigments such as alkali blue, phthalocyanine blue, cobalt blue andultramarine blue.

Meanwhile, the black iron-based particles may contain, in addition toiron and titanium, at least one element selected from the groupconsisting of K, Ca, Sr, Ba, Zr, Mg, Al, Si, P, Mn, Co, Ni, Cu, Zn orthe like, in an amount of not more than 10 atm % based on a total amountof iron and titanium.

Next, the black toner (black non-magnetic toner) of the presentinvention is described.

The black toner of the present invention comprises the black iron-basedparticles according to the present invention, and a binder resin, andmay further optionally contain a mold release agent, a colorant, acharge controller and other additives, if required.

The black toner has an average particle diameter of usually 3 to 15 μm,preferably 5 to 12 μm, and as low a magnetization value (saturationmagnetization value) as possible, e.g., usually not more than 30 Am²/kg,preferably not more than 20 Am²/kg.

The mixing ratio of the binder resin and the black iron-based particlesmay be determined such that the black iron-based particles is containedin an amount of usually 0.1 to 900 parts by weight, preferably 17 to 185parts by weight based on 100 parts by weight of the binder resin.

Examples of the binder resin may include polyester resins,styrene-acrylic copolymer resins, and vinyl-based polymers or copolymersobtained by polymerizing or copolymerizing vinyl-based monomers such asstyrene, acrylic acid alkyl esters and methacrylic acid alkyl esters.Examples of the styrene monomers may include styrene and substitutedstyrenes. Examples of the acrylic acid alkyl ester monomers may includeacrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate or thelike. The above copolymers may preferably contain styrene-basedcomponents in an amount of 50 to 95% by weight.

As the binder resin, the above vinyl-based polymers or copolymers may beused in combination with polyester-based resins, epoxy-based resins,polyurethane-based resins, etc.

The black toner of the present invention shows an image density ofimages of preferably not less than 1.25.

Next, the process for producing the black iron-based particles accordingto the present invention is described.

The black iron-based particles of the present invention can be producedby coating the surface of magnetite particles having a Fe²⁺ content ofusually 17 to 28% by weight, preferably 18 to 27% by weight (calculatedas FeO), with a titanium compound, heat-calcining the thus coatedmagnetite particles at a temperature of usually 650 to 880° C. under anon-oxidative atmosphere, and then pulverizing the thus calcinedparticles.

When the magnetite particles used in the present invention have a Fe²⁺content of less than 17% by weight (calculated as FeO), unnecessaryphases are formed in the obtained particles, resulting in deterioratedblackness thereof. It may be difficult to industrially produce magnetiteparticles having a Fe²⁺ content of more than 28% by weight.

The magnetite particles used in the present invention have an averageparticle diameter of usually 0.007 to 0.4 μm, preferably 0.01 to 0.3 μm,more preferably 0.02 to 0.2 μm, a BET specific surface area value ofusually 7.5 to 50 m²/g, preferably 8 to 30 m²/g.

The magnetite particles may be produced by ordinary methods, forexample, by passing an oxygen-containing gas through a ferrous saltreaction solution containing ferrous hydroxide colloid obtained byreacting an aqueous ferrous salt solution with an aqueous alkalisolution.

Examples of the titanium compound used in the present invention mayinclude titanyl sulfate, titanium tetrachloride, titanium trichloride orthe like.

The amount of the titanium compound added is usually 10 to 40 atm %,preferably 12 to 35 atm %, more preferably 20 to 33.3 atm % based onwhole Fe.

Upon coating the magnetite particles with the titanium compound(titanium oxide hydroxide), it is important to add the titanium compoundto a water suspension containing the magnetite particles andsimultaneously prevent the pH value of the water suspension from beinglowered, by adding an aqueous alkali hydroxide solution or an aqueousalkali carbonate solution thereto. When no alkali solution is added and,as a result, the pH value is lowered, the elution of iron may be caused,so that Fe₂TiO₅ may be formed after the calcination, resulting ininsufficient blackness of the obtained particles. However, when theNa—Fe—Ti compound is contained, the obtained particles can show asufficient blackness even though Fe₂TiO₅ is formed therein. Therefore,upon adding the titanium compound, the pH value of the water suspensionmay be lowered without addition of the alkali solution.

Meanwhile, when different kinds of metal elements are incorporated intothe black iron-based particles, these elements may be previouslycontained in the magnetite particles, or various salts of the metalelements or a solution containing these metal elements may be added tothe aqueous solution containing the magnetite particles whose surface iscoated with the titanium compound.

The heat-calcination of the present invention is performed under anon-oxidative atmosphere. Under an oxidative atmosphere, it may bedifficult to obtain the black iron-based particles having a highblackness.

The heat-calcination of the present invention is performed in atemperature range of usually 650 to 880%, preferably 700 to 850%. Whenthe heat-calcination temperature is less than 650%, the solid phasereaction between the magnetite particles and the Ti compound tends tobecome insufficient, so that it may be difficult to obtain the aimedblack iron-based particles. When the heat-calcination temperature ismore than 880%, the sintering within or between the particles tends tobe caused, resulting in production of coarse particles.

The black iron-based particles containing the Na—Fe—Ti compound can beproduced (i) by adding the titanium compound and then a sodium compoundto a water suspension containing the magnetite particles, and thendrying the thus obtained particles; or (ii) by preparing magnetiteparticles, adding a titanium compound to a water suspension containingthe magnetite particles, filtering out and water-washing the particles,and then dry-mixing the obtained particles with a sodium compound. Thethus produced black iron-based particles containing the Na—Fe—Ticompound are heat-calcined in a temperature range of 650 to 880% under anon-oxidative atmosphere, and then pulverized.

Examples of the sodium compound used in the above production method mayinclude sodium hydroxide, sodium sulfate, sodium carbonate, sodiumchloride or the like. Meanwhile, as the sodium compound, there may beused sodium hydroxide or sodium carbonate in the form of the aqueousalkali hydroxide solution or the aqueous alkali carbonate solution whichis used to allow the water suspension to maintain the pH valueimmediately after adding the titanium compound thereto without loweringupon coating the surface of the magnetite particles with the titaniumcompound (titanium oxide hydroxide).

In order to produce the black iron-based particles having the bluepigment, the blue pigment may be added to the black iron-based particlesupon pulverization thereof. In order to adhere the blue pigment onto thesurface of the black iron-based particles, the blue pigment may bebonded or coated on the surface of the respective particles composed of(1) the FeTiO₃—Fe₂O₃ solid solution or (2) the mixed composition of theFeTiO₃—Fe₂O₃ solid solution and the iron-based oxide having a spinelstructure, through a gluing agent. As the gluing agent, there may beused organosilane compounds obtainable from alkoxysilanes, orpolysiloxanes.

Next, the process for producing the black non-magnetic toner accordingto the present invention is described.

In the present invention, the black non-magnetic toner can be producedby known methods in which a predetermined amount of the binder resin anda predetermined amount of the black non-magnetic particles are subjectedto mixing, kneading and pulverization. For example, a mixture containingthe black non-magnetic particles and the binder resin, and furtheroptionally containing a mold release agent, a colorant, a chargecontroller and other additives, if required, is intimately mixed by amixer, heat-kneaded by a heating kneader to disperse the blacknon-magnetic particles, etc. in the binder resin, and then cooled andsolidified to obtain a kneaded resin material. The thus obtained kneadedresin material is then subjected to pulverization and classification toobtain particles having a desired particle diameter.

As the mixer, there may be used a Henschel mixer, a ball mill or thelike. As the heating kneader, there may be used a roll mill, a kneader,a twin-screw extruder or the like. The pulverization of particles may beperformed using a pulverizer such as a cutter mill and a jet mill, andthe classification may be performed using a known air classifier.

The black non-magnetic toner may also be produced by a suspensionpolymerization method or an emulsion polymerization method. In thesuspension polymerization method, the black non-magnetic toner may beproduced by dissolving and dispersing a mixture containing apolymerizable monomer and black magnetic iron oxide particles andfurther optionally containing a colorant, a polymerization initiator, across-linking agent, a charge controller and other additives, ifrequired, to obtain a monomer composition, adding the obtained monomercomposition to a water phase containing a suspension stabilizer whilestirring to obtain granulated particles, and then polymerizing thegranulated particles to obtain a toner having a desired particlediameter. In the emulsion polymerization method, the black non-magnetictoner may be produced by dispersing a monomer and black non-magneticparticles together with a colorant, a polymerization initiator, etc., ifrequired, in a water, and polymerizing the water dispersion while addingan emulsifier thereto to obtain a toner having a desired particlediameter.

The reason why the black iron-based particles of the present inventioncan exhibit an excellent blackness, is considered to be that sinceiron-based oxide having a spinel structure containing a large amount ofFe²⁺ is used as raw particles, the production of unnecessary phasesadversely affecting the blackness can be inhibited even when subjectingthe particles to heat-treatment.

The reason why the black iron-based particles of the present inventioncan exhibit not only an excellent blackness but also a low magnetizationvalue, is considered to be that the amount of the iron-based oxidehaving a spinel structure used is as low as possible.

Further, according to the present invention, since the blue pigment isincluded as additives in the black non-magnetic particles or adheredonto the surface of the black non-magnetic particles, the blackness andtinting strength of the obtained particles can be further enhanced.

Thus, the black iron-based particles of the present invention aresuitably used as black-colored pigments and paints, coloring materialsfor resin compositions, fillers, etc., because of an excellent blacknessand a less magnetization value thereof.

Furthermore, the black non-magnetic toner produced using the blackiron-based particles of the present invention are suitable as anon-magnetic toner since the non-magnetic toner can exhibit not only ahigh blackness but also a low magnetization value.

EXAMPLES

The present invention will now be described in more detail withreference to the following examples, but the present invention is notrestricted to those examples and various modifications are possiblewithin the scope of the invention.

Various properties were evaluated by the following methods.

(1) The average particle diameter of the respective particles isexpressed by the average value of diameters of 350 particles measured onan electron micrograph thereof.

(2) The phase constituting the particles was identified by an X-raydiffraction method (tube used: Cu). Also, the peak intensity ratiobetween FeTiO₃—Fe₂O₃ solid solution and Fe₃O₄-γ-Fe₂O₃ solid solution wasdetermined by calculating a ratio of a peak intensity of (220) plane ofthe Fe₃O₄-γ-Fe₂O₃ solid solution to a peak intensity of (104) plane ofthe FeTiO₃—Fe₂O₃ solid solution.

(3) The specific surface area value of the particles was measured by aBET method using “Mono Sorb MS-II” (manufactured by Yuasa Ionics Co.,Ltd.).

(4) The magnetic properties of the black iron-based particles weremeasured under a magnetic field of 796 kA/m (10 kOe) using a vibrationsample magnetometer “VSM-3S-15” (manufactured by Toei Kogyo Co., Ltd.).

(5) The contents of metal elements such as Ti, Al, Si, K and Cu whichwere contained in the black iron-based particles, were measured by acalibration curve method using a “Fluorescent X-ray Analyzer RIX-2100Model” (manufactured by Rigaku Denki Kogyo Co., Ltd.).

(6) The Fe²⁺ content is expressed by the value measured by the followingchemical analysis method.

That is, 25 cc of a mixed solution containing phosphoric acid andsulfuric acid at a mixing ratio of 2:1 was added to 0.5 g of blackmagnetic iron oxide particles or black iron-based particles under aninert gas atmosphere to dissolve the black magnetic iron oxide particlesor black iron-based particles therein. The thus obtained solution wasdiluted, and several droplets of diphenylamine sulfonic acid as anindicator were dropped to the diluted solution. Then, the obtainedsolution was subjected to oxidation-reduction titration using an aqueouspotassium bichromate solution. The Fe²⁺ content was calculated from theamount of the aqueous potassium bichromate solution used until reachinga terminal point at which the above diluted solution exhibited a violetcolor.

(7) The blackness of the black iron-based particles was measured asfollows.

That is, 0.5 g of a sample and 0.5 ml of castor oil were intimatelykneaded together by a Hoover's muller to form a paste. 4.5 g of a clearlacquer was added to the obtained paste and was intimately kneaded toform a paint. The obtained paint was applied on a cast-coated paper byusing a 150 μm (6-mil) applicator to produce a coating film piece(having a film thickness of about 30 μm). The color of the thus obtainedcoating film piece was measured by a spectro-colorimeter “COLOR GUIDE”(manufactured by BYK-Gardner GmbH), and the blackness thereof wasexpressed by a color specification index (L* value) according to JIS Z8929.

(8) The tinting strength of the black iron-based particles was measuredas follows.

That is, 0.5 g of a sample, 0.5 ml of castor oil and 1.5 g of titaniumdioxide were intimately kneaded together by a Hoover's muller to form apaste. 4.5 g of a clear lacquer was added to the obtained paste and wasintimately kneaded to form a paint. The obtained paint was applied on acast-coated paper by using a 150 μm (6-mil) applicator to produce acoating film piece (having a film thickness of about 30 μm). The colorof the thus obtained coating film piece was measured by aspectro-colorimeter “COLOR GUIDE” (manufactured by BYK-Gardner GmbH),and the tinting strength thereof was expressed by a color specificationindex (L* value) according to JIS Z 8929.

(9) The image density of images obtained using the black toner wasdetermined by printing a solid black (A4) with the prepared black tonerusing an electrophotographic printer “MICROLINE 600CL” (manufactured byOki Denki Kogyo Co., Ltd.) and then measuring an image density of thesolid black using by an image density-measuring device (tradename:“RD914”, manufactured by MACBETH Co., Ltd.). The larger the measuredvalue, the more excellent the image density.

(10) The fogging caused by the black toner was evaluated as follows.

That is, the same solid black (A4) as used above for measuring theblackness of the electrophotographic toner was visually observed todetermine whether or not any fogging was caused thereon. The results areclassified into the following four ranks.

-   -   A: Excellent (no fogging)    -   B: Good (substantially no fogging)    -   C: Still usable (slight fogging)    -   D: unusable

Example 1

Production of Black Iron-Based Particles

An aqueous solution containing 38.9 mol of titanyl sulfate(corresponding to 30 atm % (calculated as Ti) based on whole Fecontained in magnetite particles) was added to a water suspensioncontaining 10 kg of spherical magnetite particles (average particlediameter: 0.15 μm; BET specific area: 10.8 m²/g; FeO content: 25.6% byweight). Meanwhile, upon the addition, an aqueous NaOH solution wasadded to the resultant mixed solution so as not to lower the pH value ofthe reaction solution. Then, after adjusting the pH value of the mixedsolution to 8.0 to precipitate and deposit titanium oxide hydroxide onthe surface of the magnetite particles, the obtained particles werefiltered out, washing and then dried to obtain spherical black magneticiron oxide particles whose surface was coated with the titanium oxidehydroxide.

10 kg of the thus obtained spherical black magnetic iron oxide particleswhose surface was coated with the titanium oxide hydroxide wereheat-calcined under a N₂ gas flow at 750% for 60 minutes, and thenpulverized to obtain black iron-based particles.

As a result, it was confirmed that the thus obtained black iron-basedparticles had a Ti content of 29.9 atm % based on whole Fe, a saturationmagnetization value σs of 10.5 Am²/kg, a blackness (L* value) of 9.7, atinting strength of 40.4, and an average particle diameter 0.17 μm asshown in the electron micrograph of FIG. 1. In addition, as shown in theX-ray diffraction pattern of FIG. 2, the black iron-based particles werecomposed of a mixed composition of FeTiO₃—Fe₂O₃ solid solution andFe₃O₄-γ-Fe₂O₃ solid solution, and the ratio of a peak intensity of (220)plane of FeTiO₃—Fe₂O₃ to a peak intensity of (104) plane of FeTiO₃—Fe₂O₃solid was 1:0.09.

Production of Electrophotographic Black Toner

The above prepared black iron-based particles were mixed with thefollowing components at a mixing ratio shown below using a Henschelmixer, and the obtained composition was melt-kneaded by a twin-screwextrusion kneader (tradename: “S-1” manufactured by Kurimoto TekkoshaCo., Ltd.). The obtained kneaded material was cooled, finely pulverizedand then classified to separate particles having an volume-averageparticle diameter of 8 to 10 μm (measured using “Multisizer” (tradename)manufactured by Coulter Counter Co., Ltd.), thereby obtaining tonerparticles. Further, 0.5 part by weight of hydrophobic finer silicapowder (tradename “RX-200” produced by Nippon Aerojil Co., Ltd.) wasexternally added to 100 parts by weight of the thus obtained tonerparticles, thereby obtaining an electrophotographic black toner.

Composition: Styrene-acrylic copolymer 100 parts by weight resin(“HI-MER SB-308” produced by Sanyo Kasei Kogyo Co., Ltd.) Blackiron-based particles  25 parts by weight Negative charge controller  0.5part by weight (“BONTRON E-84” produced by Orient Kagaku Kogyo Co.,Ltd.) Low-molecular weight wax  5 parts by weight (“BISCOL 550-P”produced by Sanyo Kasei Kogyo Co., Ltd.)

As a result, it was confirmed that the thus obtained electrophotographicblack toner had an initial image density of 1.45 and was free fromfogging (rank: A in four-rank evaluation).

Examples 2 to 12 and Comparative Examples 2 to 8

The same procedure as defined in Example 1 was conducted except thatkind of magnetite, amount of the titanium compound added andheat-calcination treatment temperature were changed variously, therebyobtaining black iron-based particles.

The essential production conditions are shown in Table 1, and variousproperties of the obtained black non-magnetic particles are shown inTable 2.

Comparative Example 1 Follow-up test of Example 1 of Japanese PatentApplication Laid-Open (KOKAI) No. 3-2276(1991)

100 g of granular magnetite particles (average particle diameter: 0.2μm; magnetization value: 85.0 emu/g) were mixed and dispersed in anaqueous solution containing 0.26 mol of TiOSO₄ (corresponding toTi/Fe=20.0 atm %). Then, the obtained mixed solution was neutralized byadding NaOH thereto, and the pH value thereof was adjusted to 8, therebyprecipitating and depositing a hydroxide of Ti on the surface of themagnetite particles. Thereafter, the thus obtained particles werefiltered out and then dried. As a result of fluorescent X-ray analysis,it was confirmed that the obtained granular magnetite particles whosesurface was coated with the hydroxide of Ti had a Ti (IV) content of21.0 atm % based on a sum of Fe (II) and Fe (III).

50 g of the thus obtained granular magnetite particles whose surface wascoated with the hydroxide of Ti were heat-calcined under a N₂ gas flowat 750% for 120 minutes, and then pulverized to obtain black particles.

As a result, it was confirmed that the obtained black particles had a Ticontent of 21.0 atm % based on whole Fe, a saturation magnetizationvalue σs of 0.6 Am²/kg, a blackness (L* value) of 14.1, a tintingstrength of 46.9 and an average particle diameter of 0.25 μm, and thatas shown in the X-ray diffraction pattern of FIG. 3, the black particleswere composed of a mixed composition of Fe₂O₃—FeTiO₃ solid solution andFe₂TiO₅.

The essential production conditions are shown in Table 1, and variousproperties of the obtained black iron-based particles are shown in Table2.

Meanwhile, in Comparative Examples 6 and 7, in addition to the mixedcomposition of Fe₂O₃—FeTiO₃ and Fe₂O₃, unreacted titanium compoundremained in the obtained particles.

Examples 13 to 17

The same procedures as defined in Examples 1 to 5 were conducted exceptthat the respective blue pigments were added upon the pulverizationtreatment, thereby obtaining black non-magnetic particles.

The essential production conditions and various properties of theobtained black iron-based particles are shown in Table 3.

Examples 18 to 33 and Comparative Examples 10 to 16

Production of Black Toner

The same procedure as defined in Example 1 was conducted except thatkind of the black non-magnetic particles was changed variously, therebyobtaining black toners.

The essential treatment conditions and various properties of theobtained black toners are shown in Tables 4 and 5.

Example 34

Production of Black Iron-Based Particles

An aqueous solution containing 37.6 mol of titanyl sulfate(corresponding to 29 atm % (calculated as Ti) based on whole Fecontained in magnetite particles) was added to a water suspensioncontaining 10 kg of spherical magnetite particles (average particlediameter: 0.15 μm; BET specific area: 10.8 m²/g). Then, after adjustingthe pH value of the resultant mixed solution to 8.0 to precipitate anddeposit titanium oxide hydroxide on the surface of the magnetiteparticles, the obtained particles were filtered out, washed with waterand then dried.

The thus obtained spherical black magnetic iron oxide particles whosesurface was coated with the titanium oxide hydroxide were mixed with 420g of sodium sulfate. Then, 10 kg of the thus obtained mixture washeat-calcined under a N₂ gas flow at 750% for 60 minutes and thenpulverized to obtain black iron-based particles.

As a result, it was confirmed that the thus obtained black iron-basedparticles had a Ti content of 29.8 atm % based on whole Fe, a saturationmagnetization value σs of 12 Am²/kg, a blackness (L* value) of 9.2, atinting strength of 40.2 and a BET specific surface area of 8.5 m²/g. Inaddition, as shown in the X-ray diffraction pattern of FIG. 4, the blackiron-based particles were composed of a mixed composition ofFeTiO₃—Fe₂O₃ solid solution, Fe₃O₄-γ-Fe₂O₃ solid solution and NaFeTi₃O₈,and the ratio of a main peak (peak at a spacing (d) of 3.63 Å) intensityof NaFeTi₃O₈ to a peak intensity of (104) plane of FeTiO₃—Fe₂O₃ was0.08:1.

Production of Electrophotographic Toner

The above prepared black iron-based particles were mixed with thefollowing components at a mixing ratio shown below using a Henschelmixer, and the obtained composition was melt-kneaded by a twin-screwextrusion kneader (tradename: “S-1” manufactured by Kurimoto TekkoshaCo., Ltd.). The obtained kneaded material was cooled, finely pulverizedand then classified to separate particles having an volume-averageparticle diameter of 8 to 10 μm (measured using “Multisizer” (tradename)manufactured by Coulter Counter Co., Ltd.), thereby obtaining tonerparticles. Further, 0.5 part by weight of hydrophobic finer silicapowder (tradename “RX-200” produced by Nippon Aerojil Co., Ltd.) wasexternally added to 100 parts by weight of the thus obtained tonerparticles, thereby obtaining an electrophotographic toner.

Composition: Styrene-acrylic copolymer 100 parts by weight resin(“HI-MER SB-308” produced by Sanyo Kasei Kogyo Co., Ltd.) Blackiron-based particles  25 parts by weight Negative charge controller  0.5part by weight (“BONTRON E-84” produced by Orient Kagaku Kogyo Co.,Ltd.) Low-molecular weight wax  5 parts by weight (“BISCOL 550-P”produced by Sanyo Kasei Kogyo Co., Ltd.)

As a result, it was confirmed that the thus obtained electrophotographictoner had an initial image density of 1.45 and was free from fogging(rank: A in four-rank evaluation).

The essential production conditions are shown in Table 6, and variousproperties of the obtained black non-magnetic particles are shown inTable 7.

Examples 35 and 36

The same procedure as defined in Example 34 was conducted except thatkind of magnetite, amount of the titanium compound added, amount of thesodium compound added and heat-calcination treatment temperature werechanged variously, thereby producing black iron-based particles.

The essential production conditions are shown in Table 6, and variousproperties of the obtained black iron-based particles are shown in Table7.

Example 37

The same procedure as defined in Example 34 was conducted except thatthe blue pigment was added upon the pulverization treatment, therebyobtaining black non-magnetic particles.

Various properties of the obtained black non-magnetic particles areshown in Table 8.

Examples 38 and 41

Production of Black Toner

The same procedure as defined in Example 34 was conducted except thatkind of the black non-magnetic particles was changed variously, therebyobtaining black toners.

The essential treatment conditions and various properties of theobtained black toners are shown in Table 9. TABLE 1 Properties ofmagnetite particles Average Examples and particle Comparative diameterExamples Kind (μm) Example 1 Spherical magnetite 0.15 Example 2Spherical magnetite 0.18 Example 3 Spherical magnetite 0.15 Example 4Spherical magnetite 0.10 Example 5 Spherical magnetite 0.10 Example 6Spherical magnetite 0.04 Example 7 Spherical magnetite 0.10 Example 8Spherical magnetite 0.15 Example 9 Spherical magnetite 0.15 Example 10Octahedral magnetite 0.17 Example 11 Octahedral magnetite 0.17 Example12 Spherical magnetite 0.18 Comparative Granular magnetite 0.20 Example1 Comparative Spherical magnetite 0.10 Example 2 Comparative Sphericalmagnetite 0.02 Example 3 Comparative Spherical magnetite 0.23 Example 4Comparative Spherical magnetite 0.15 Example 5 Comparative Sphericalmagnetite 0.15 Example 6 Comparative Spherical magnetite 0.15 Example 7Comparative Spherical magnetite 0.15 Example 8 Properties of magnetiteparticles Saturation BET specific magnetization Examples and surfacearea FeO value Comparative value content σs Examples (m²/g) (wt %)(Am²/kg) Example 1 10.8 25.6 82 Example 2 9.7 26.0 83 Example 3 10.825.6 82 Example 4 14.8 25.1 82 Example 5 14.8 25.1 82 Example 6 29.718.2 80 Example 7 14.8 25.1 82 Example 8 10.8 25.6 82 Example 9 10.825.6 82 Example 10 8.1 26.7 85 Example 11 8.1 26.7 85 Example 12 9.726.0 83 Comparative 7.9 16.5 85 Example 1 Comparative 14.7 13.4 80Example 2 Comparative 52.3 10.7 75 Example 3 Comparative 7.1 26.2 88Example 4 Comparative 10.8 25.6 82 Example 5 Comparative 10.8 25.6 82Example 6 Comparative 10.8 25.6 82 Example 7 Comparative 10.8 25.6 82Example 8 Coating treatment Different kinds of Examples with Ti compoundmetal elements and Ti/ Amount Comparative whole Fe added Examples Kind(atm %) Kind (atm %) Example 1 TiOSO₄ 30 — — Example 2 TiCl₄ 30 — —Example 3 TiOSO₄ 21 — — Example 4 TiCl₄ 26 — — Example 5 TiOSO₄ 12 — —Example 6 TiCl₄ 35 — — Example 7 TiCl₄ 30 Si 1 Example 8 TiOSO₄ 30 Cu 5Example 9 TiOSO₄ 24 Al 8 Example 10 TiCl₄ 30 — — Example 11 TiCl₄ 35 — —Example 12 TiCl₄ 30 K 1 Comparative TiOSO₄ 20 — Example 1 ComparativeTiCl₄ 30 — — Example 2 Comparative TiOSO₄ 30 — — Example 3 ComparativeTiOSO₄ 30 — — Example 4 Comparative TiOSO₄ 8 — — Example 5 ComparativeTiOSO₄ 50 — — Example 6 Comparative TiCl₄ 30 — — Example 7 ComparativeTiCl₄ 30 — — Example 8 Examples and Heat-treatment ComparativeTemperature Time Examples (° C.) (min) Example 1 750 60 Example 2 750 60Example 3 750 60 Example 4 750 60 Example 5 750 60 Example 6 750 60Example 7 750 60 Example 8 750 60 Example 9 750 60 Example 10 750 60Example 11 770 60 Example 12 750 60 Comparative 750 120 Example 1Comparative 750 60 Example 2 Comparative 750 60 Example 3 Comparative750 60 Example 4 Comparative 750 60 Example 5 Comparative 750 60 Example6 Comparative 600 60 Example 7 Comparative 900 60 Example 8

TABLE 2 Properties of black iron-based particles Average Examples andparticle Comparative diameter Examples (μm) Composition Example 1 0.17Fe₂O₃—FeTiO₃ + Fe₃O₄-γ-Fe₂O₃ Example 2 0.20 Fe₂O₃—FeTiO₃ + Fe₃O₄-γ-Fe₂O₃Example 3 0.16 Fe₂O₃—FeTiO₃ + Fe₃O₄-γ-Fe₂O₃ Example 4 0.12Fe₂O₃—FeTiO₃ + Fe₃O₄-γ-Fe₂O₃ Example 5 0.11 Fe₂O₃—FeTiO₃ + Fe₃O₄-γ-Fe₂O₃Example 6 0.08 Fe₂O₃—FeTiO₃ Example 7 0.11 Fe₂O₃—FeTiO₃ + Fe₃O₄-γ-Fe₂O₃Example 8 0.17 Fe₂O₃—FeTiO₃ + Fe₃O₄-γ-Fe₂O₃ Example 9 0.18Fe₂O₃—FeTiO₃ + Fe₃O₄-γ-Fe₂O₃ Example 10 0.19 Fe₂O₃—FeTiO₃ +Fe₃O₄-γ-Fe₂O₃ Example 11 0.21 Fe₂O₃—FeTiO₃ Example 12 0.21Fe₂O₃—FeTiO₃ + Fe₃O₄-γ-Fe₂O₃ Comparative 0.25 Fe₂O₃—FeTiO₃ + Fe₂TiO₅Example 1 Comparative 0.12 Fe₂O₃—FeTiO₃ + Fe₂TiO₅ Example 2 Comparative0.15 Fe₂O₃—FeTiO₃ + Fe₂TiO₅ Example 3 Comparative 0.26 Fe₂O₃—FeTiO₃ +Fe₃O₄-γ-Fe₂O₃ Example 4 Comparative 0.11 Fe₂O₃—FeTiO₃ + Fe₃O₄-γ-Fe₂O₃Example 5 Comparative 0.18 Fe₂O₃—FeTiO₃ + Fe₃O₄-γ-Fe₂O₃ Example 6Comparative 0.12 Fe₂O₃—FeTiO₃ + Fe₃O₄-γ-Fe₂O₃ Example 7 Comparative 0.25Fe₂O₃—FeTiO₃ + Fe₂TiO₅ Example 8 Properties of black iron-basedparticles Different kinds of Examples and Peak Ti/ metal Comparativeintensity whole Fe elements Examples ratio (atm %) (atm %) Example 11:0.09 29.9 — Example 2 1:0.12 29.8 — Example 3 1:0.29 21.8 — Example 41:0.22 25.7 — Example 5 1:0.40 12.0 — Example 6 — 34.6 — Example 71:0.08 29.6 Si: 1.0 Example 8 1:0.07 29.8 Cu: 4.8 Example 9 1:0.07 23.9Al: 7.9 Example 10 1:0.15 29.9 — Example 11 — 35 — Example 12 1:0.1029.9 K: 1.0 Comparative — 21.0 — Example 1 Comparative — 29.8 — Example2 Comparative — 29.9 — Example 3 Comparative 1:0.14 30.0 — Example 4Comparative 1:0.41 7.9 — Example 5 Comparative 1:0.20 49.3 — Example 6Comparative 1:0.47 30.0 — Example 7 Comparative — 29.8 — Example 8Properties of black iron-based particles BET Examples specificSaturation and surface magnetization Comparative area value valueBlackness Tinting Examples (m²/g) (Am²/kg) (L* value) strength Example 19.0 10.5 9.7 40.4 Example 2 7.1 14.9 9.2 41.3 Example 3 10.2 32.0 9.338.7 Example 4 11.8 21.8 9.9 39.6 Example 5 13.2 38.8 10.7 38.9 Example6 18.7 5.8 12.3 40.9 Example 7 13.0 11.2 10.3 39.8 Example 8 8.8 9.1 8.939.0 Example 9 8.1 9.3 11.1 41.2 Example 10 7.6 16.6 9.5 41.0 Example 116.8 0.3 12.5 42.5 Example 12 6.9 13.0 8 41.4 Comparative 5.8 0.6 14.146.9 Example 1 Comparative 12.6 0.2 14.3 46.2 Example 2 Comparative 10.10.4 16.5 44.4 Example 3 Comparative 5.2 15.2 9.1 46.0 Example 4Comparative 14.0 42.4 11.0 41.9 Example 5 Comparative 12.2 4.6 15.2 48.1Example 6 Comparative 14.1 46.9 16.0 51.2 Example 7 Comparative 5.6 1.813.8 46.8 Example 8

TABLE 3 Iron- Blue pigment titanium Amount composite added Examplesoxide Kind (wt %) Example 13 Example 2 Cu 5 phthalocyanine Example 14Example 3 Alkali blue 10 Example 15 Example 4 Alkali blue 0.5 Example 16Example 5 Cu 10 phthalocyanine Example 17 Example 6 Cu 3 phthalocyanineBET specific Saturation Existing surface magnetization condition of areavalue value Examples blue pigment (m²/g) (Am²/kg) Example 13 Surfacecoat 7.4 13.8 Example 14 Included 16.3 28.9 Example 15 Surface coat 11.721.7 Example 16 Surface coat 13.8 35.0 Example 17 Included 19.9 5.6Blackness Examples (L* value) Tinting strength Example 13 7.7 39.7Example 14 6.8 35.2 Example 15 9.4 38.9 Example 16 8.2 36.5 Example 1710.8 40.6

TABLE 4 Properties of toner Saturation Black iron-based magnetizationvalue Examples particles used (Am²/kg) Example 1 Example 1 2.0 Example18 Example 2 2.9 Example 19 Example 3 6.1 Example 20 Example 4 4.2Example 21 Example 5 7.4 Example 22 Example 6 1.1 Example 23 Example 72.1 Example 24 Example 8 1.7 Example 25 Example 9 1.8 Example 26 Example10 3.2 Example 27 Example 11 0.1 Example 28 Example 12 2.5 Example 29Example 13 2.6 Example 30 Example 14 5.5 Example 31 Example 15 4.2Example 32 Example 16 6.7 Example 33 Example 17 1.1 Properties of tonerInitial image Examples density Fogging Example 1 1.45 A Example 18 1.40A Example 19 1.50 B Example 20 1.45 B Example 21 1.50 B Example 22 1.45B Example 23 1.45 A Example 24 1.50 A Example 25 1.40 A Example 26 1.40A Example 27 1.40 A Example 28 1.45 A Example 29 1.45 A Example 30 1.60B Example 31 1.50 B Example 32 1.60 B Example 33 1.40 B

TABLE 5 Properties of toner Saturation Comparative Black iron-basedmagnetization value Examples particles used (Am²/kg) ComparativeComparative Example 1 0.1 Example 9 Comparative Comparative Example 20.0 Example 10 Comparative Comparative Example 3 0.1 Example 11Comparative Comparative Example 4 4.6 Example 12 Comparative ComparativeExample 5 8.1 Example 13 Comparative Comparative Example 6 0.9 Example14 Comparative Comparative Example 7 9.0 Example 15 ComparativeComparative Example 8 0.3 Example 16 Properties of toner ComparativeInitial image Examples density Fogging Comparative 1.15 A Example 9Comparative 1.15 A Example 10 Comparative 1.25 B Example 11 Comparative1.05 A Example 12 Comparative 1.20 C Example 13 Comparative 1.10 BExample 14 Comparative 1.00 — Example 15 Comparative 1.15 A Example 16

TABLE 6 Properties of magnetite particles Average particle diameterExamples Kind (μm) Example 34 Spherical magnetite 0.15 Example 35Spherical magnetite 0.15 Example 36 Spherical magnetite 0.18 Propertiesof magnetite particles Saturation BET specific magnetization surfacearea value value FeO content σs Examples (m²/g) (wt %) (Am²/kg) Example34 10.8 25.6 82 Example 35 10.8 25.6 82 Example 36 9.7 26.0 83 Coatingtreatment with Ti compound Na compound added Kind of Ti/ Amount Ti wholeFe added Examples compound (atm %) Kind (g) Example 34 TiOSO₄ 30 sodium420 sulfate Example 35 TiOSO₄ 32 sodium 100 carbonate Example 36 TiCl₄20 sodium 840 sulfate Different kinds of metal elements AmountHeat-treatment added Temperature Time Examples Kind (atm %) (° C.) (min)Example 34 — — 750 60 Example 35 — — 750 60 Example 36 — — 750 60

TABLE 7 Properties of black iron-based particles Average particlediameter Examples (μm) Composition Example 34 0.16 Fe₂O₃—FeTiO₃ +Fe₃O₄-γ-Fe₂O₃ + NaFeTi₃O₈ Example 35 0.18 Fe₂O₃—FeTiO₃ + Fe₂TiO₅ +NaFeTi₃O₈ Example 36 0.17 Fe₂O₃—FeTiO₃ + Fe₃O₄-γ-Fe₂O₃ + NaFeTi₃O₈Properties of black iron-based particles Ratio of peak intensity of(220) Ratio of main peak plane of Fe₃O₄-γ- intensity of Fe₂O₃ solidsolution NaFeTi₃O₈ to peak to peak intensity intensity of (104) of (104)plane of plane of Fe₂O₃— Fe₂O₃—FeTiO₃ solid FeTiO₃ solid Examplessolution solution Example 34 1:0.12 0.08:1 Example 35 — 0.04:1 Example36 1:0.52 0.32:1 Properties of black iron-based particles Differentkinds of BET specific Ti/ metal surface area whole Fe elements valueExamples (atm %) (atm %) (m²/g) Example 34 29.8 — 8.5 Example 35 32 —8.0 Example 36 20.5 — 9.0 Properties of black iron-based particlesSaturation magnetization value Blackness Tinting Examples (Am²/kg) (L*value) strength Example 34 12.0 9.2 40.2 Example 35 0.2 10.5 40.9Example 36 57.0 8.5 40.5

TABLE 8 Iron- Blue pigment titanium Amount composite added Examplesoxide Kind (wt %) Example 37 Example 34 Cu 5 phthalocyanine BET specificSaturation Existing surface magnetization condition of area value valueExamples blue pigment (m²/g) (Am²/kg) Example 37 Surface coat 8.8 11.4Blackness Examples (L* value) Tinting strength Example 37 7.2 38.0

TABLE 9 Properties of toner Saturation Black non-magnetic magnetizationvalue Examples particles used (Am²/kg) Example 38 Example 34 2.3 Example39 Example 35 0 Example 40 Example 36 10.9 Example 41 Example 37 2.2Properties of toner Initial image Examples density Fogging Example 381.50 A Example 39 1.45 A Example 40 1.60 B Example 41 1.65 A

1. Black iron-based particles comprising a FeTiO₃—Fe₂O₃ solid solutionor a mixed composition of a FeTiO₃—Fe₂O₃ solid solution and aniron-based oxide having a spinel structure, and having a Ti content offrom more than 10.0 atm % to 40.0 atm %, calculated as Ti, based onwhole Fe, and a blackness (L* value) of 6 to
 13. 2. Black iron-basedparticles according to claim 1, wherein said iron-based oxide having aspinel structure is contained in such an amount that a ratio of a peakintensity of (220) plane of Fe₃O₄-γ-Fe₂O₃ constituting the iron-basedoxide having a spinel structure to a peak intensity of (104) plane ofFeTiO₃—Fe₂O₃ is 1:0.5 or less, when measured by an X-ray diffractionmethod.
 3. Black iron-based particles according to claim 2, wherein saidratio of a peak intensity of (220) plane of Fe₃O₄-γ-Fe₂O₃ constitutingthe iron-based oxide having a spinel structure to a peak intensity of(104) plane of FeTiO₃—Fe₂O₃ is 1:0.01 to 1:0.45.
 4. Black iron-basedparticles according to claim 1, wherein said black iron-based particleshave a saturation magnetization value of not more than 60 Am²/kg and anaverage particle diameter of 0.01 to 0.50 μm.
 5. Black iron-basedparticles according to claim 1, wherein said black iron-based particleshave a Ti content of 20 to 33.3 atm %, calculated as Ti, based on wholeFe, a saturation magnetization value of 0.1 to 40 Am²/kg, a blackness(L* value) of 6 to 12.5 and an average particle diameter of 0.04 to 0.24μm.
 6. Black iron-based particles according to claim 1, wherein saidblack iron-based particles have a BET specific surface area value of 6to 30 m²/g and a tinting strength of 35 to
 45. 7. Black iron-basedparticles according to claim 1, which further comprise a Na—Fe—Ticompound.
 8. Black iron-based particles according to claim 7, whereinsaid Na—Fe—Ti compound is contained in such an amount that a ratio of amain peak intensity of the Na—Fe—Ti compound to a peak intensity of(104) plane of FeTiO₃—Fe₂O₃ is 0.01:1 to 1.00:1, when measured by anX-ray diffraction method.
 9. Black iron-based particles according toclaim 7, wherein said Na—Fe—Ti compound is NaFeTi₃O₈, NaFeTiO₄ orNa_(0.75)Fe_(0.75)Ti_(0.25)O₂.
 10. Black iron-based particles accordingto claim 7, wherein said black iron-based particles have a saturationmagnetization value of 0.1 to 60 Am²/kg.
 11. Black iron-based particlesaccording to claim 1, which further comprise a blue pigment in an amountof 0.1 to 20% by weight.
 12. Black iron-based particles according toclaim 11, wherein said black iron-based particles have a blackness (L*value) of 6 to 12 and a tinting strength of 30 to
 42. 13. Blackiron-based particles a FeTiO₃—Fe₂O₃ solid solution or a mixedcomposition of a FeTiO₃—Fe₂O₃ solid solution and an iron-based oxidehaving a spinel structure, and having a Ti content of from more than10.0 atm % to 40.0 atm %, calculated as Ti, based on whole Fe, ablackness (L* value) of 6 to 13, a saturation magnetization value of 5to 40 Am²/kg and an average particle diameter of 0.04 to 0.24 Am. 14.Black iron-based particles comprising: a FeTiO₃—Fe₂O₃ solid solution ora mixed composition of a FeTiO₃—Fe₂O₃ solid solution and an iron-basedoxide having a spinel structure, and a Na—Fe—Ti compound, and having aTi content of from more than 10.0 atm % to 40.0 atm %, calculated as Ti,based on whole Fe, a saturation magnetization value of 0.1 to 60 Am²/kg,a blackness (L* value) of 6 to 13 and an average particle diameter of0.04 to 0.24 μm, said Na—Fe—Ti compound being contained in such anamount that a ratio of a main peak intensity of the Na—Fe—Ti compound toa peak intensity of (104) plane of FeTiO₃—Fe₂O₃ is 0.01:1 to 1.00:1,when measured by an X-ray diffraction method.
 15. Black iron-basedparticles comprising: (1) 80 to 99.9 parts by weight of a FeTiO₃—Fe₂O₃solid solution or a mixed composition of a FeTiO₃—Fe₂O₃ solid solutionand an iron-based oxide having a spinel structure; and (2) 0.1 to 20parts by weight of a blue pigment, and having a Ti content of from morethan 10.0 atm % to 40.0 atm %, calculated as Ti, based on whole Fe, asaturation magnetization value of 5 to 40 Am²/kg, a blackness (L* value)of 6 to 13 and an average particle diameter of 0.04 to 0.24 μm. 16.Black iron-based particles according to claim 13, wherein saidiron-based oxide having a spinel structure is contained in such anamount that a ratio of a peak intensity of (220) plane of Fe₃O₄-γ-Fe₂O₃constituting the iron-based oxide having a spinel structure to a peakintensity of (104) plane of FeTiO₃—Fe₂O₃ is 1:0.5 or less, when measuredby an X-ray diffraction method.
 17. A black non-magnetic tonercomprising a binder resin and the black iron-based particles as definedin claim 1.